CN115041190A - Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use - Google Patents

Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use Download PDF

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Publication number
CN115041190A
CN115041190A CN202210523196.7A CN202210523196A CN115041190A CN 115041190 A CN115041190 A CN 115041190A CN 202210523196 A CN202210523196 A CN 202210523196A CN 115041190 A CN115041190 A CN 115041190A
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catalyst
hydrotalcite
lignin
hydrogenolysis
dispersion
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李占库
王海涛
闫洪雷
吴胜华
雷智平
任世彪
颜井冲
王知彩
水恒福
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Anhui University of Technology AHUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring

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Abstract

The invention discloses hydrotalcite topology transformation high-dispersion Ni-Ru/Al 2 O 3 Preparation and application of the catalyst belong to the field of catalytic hydrogenolysis of biomass. The catalyst of the invention takes NiAl hydrotalcite as a precursor, adopts an exogenous method to introduce Ru, and prepares high-dispersion Ni-doped material through topological transformation and in-situ reductionRu/Al 2 O 3 The catalyst comprises 20-40% of Ni and 1-5% of Ru by total mass of the catalyst respectively. The highly dispersed Ni-Ru/Al 2 O 3 The catalyst shows excellent catalytic performance in hydrogenolysis reaction of lignin and a model compound thereof, can break aromatic ether bonds in the lignin and the model compound thereof with high selectivity and high activity under mild conditions, and is obviously superior to a commercial Ru/C catalyst. The catalyst provided by the invention is simple in preparation method and good in stability, does not need additional hydrogen for catalyzing hydrogenolysis reaction of lignin and model compounds thereof, and is mild in reaction conditions, so that the catalyst has a good application prospect in the lignin conversion process.

Description

Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its application
Technical Field
The invention belongs to the field of catalytic hydrogenolysis of biomass, and particularly relates to Ni-Ru/Al with high dispersion, high activity and high stability 2 O 3 A catalyst, a preparation method thereof and application in lignin hydrogenolysis.
Background
With the decreasing of fossil energy and the problem of environmental pollution, biomass resources attract people's attention. Lignin is second only to cellulose in biomass and is the only renewable aromatic source in nature. During the process of refining biomass or pulping and papermaking, a large amount of lignin waste liquor is generated. Therefore, efficient use of lignin is critical to improving the economics of biomass refining or pulp and paper making. At present, the methods for depolymerizing lignin mainly comprise pyrolysis, hydrogenolysis, oxidation, hydrolysis and the like. Compared with other depolymerization methods, hydrogenolysis has the advantages of mild reaction conditions, high product yield, adjustable composition structure and the like, and is widely concerned.
The low-carbon alcohol has the advantages of strong hydrogen supply capability, low supercritical point, easy recovery and the like, and is widely used for preparing platform compounds such as aromatic hydrocarbon, phenol, cyclohexanol, cyclane and the like by hydrogenolysis of lignin. Research shows that Ru/C and Ni-based and bimetallic catalysts can promote lignin hydrogenolysis. However, the traditional bimetallic supported catalyst is mostly prepared by an impregnation method or a coprecipitation method, and has the advantages of low dispersity, low activity and easy coking and deactivation. In recent years, hydrotalcite has been attracting much attention as a catalyst precursor for preparing a highly dispersed supported catalyst due to its structure-tunable denaturation and topology change property. Therefore, the highly dispersed Ni-Ru bimetallic catalyst is prepared by hydrotalcite topological transformation, and the catalytic hydrogenolysis of lignin to prepare the platform compound has important significance for the efficient utilization of lignin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the Ni-Ru/Al with high dispersion, high activity and high stability 2 O 3 The catalyst and the application thereof in catalyzing the hydrogenolysis of lignin are expected to realize the high-efficiency hydrogenolysis of the lignin and the model compound thereof.
The invention is realized by the following technical scheme.
The catalyst of the invention takes NiRu alloy as a catalytic active site, and Al 2 O 3 The Ni-Ru composite material is a carrier, the average grain diameter is 5.8nm, and strong electronic interaction exists between Ni and Ru; based on the total mass of the catalyst, the proportion of Ni and Ru is 20-40% and 1-5% respectively.
The invention provides a preparation method of the catalyst, which specifically comprises the following steps:
(1) taking 0.01-0.03mol of Ni (NO) 3 ) 2 ·6H 2 O、0.05-0.15mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.05-0.1mol of urea, stirring and reacting at 90-140 ℃ for 9-24h, centrifuging, washing, filtering and then drying in vacuum to obtain NiAl hydrotalcite;
(2) taking 0.4-0.6g of NiAl hydrotalcite obtained in the step (1) and 0.5-0.8g of RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain NiRuAlA hydrotalcite precursor;
(3) by H 2 Directly reducing the NiRuAl hydrotalcite obtained in the step (2), cooling and then using 1% of O 2 Passivating for 1-3h to obtain a target product: Ni-Ru/Al 2 O 3 A catalyst.
Further, H in the step (3) 2 The reduction heating rate is 2 ℃/min, the reduction temperature is 450 ℃ and 600 ℃, and the reduction time is 4-8 h.
The invention also provides the application of the catalyst prepared by the method in the hydrogenolysis of lignin and a model compound thereof, and the method comprises the following steps:
mixing Ni-Ru/Al 2 O 3 Adding the catalyst, the hydrogen source and the substrate into a reaction kettle according to the dosage ratio of 20-50mg:5-20mL:50mg, sealing, filling protective gas of 1MPa, and reacting at the temperature of 100 ℃ and 240 ℃ for l-8h to obtain the hydrogenolysis product. The hydrogen source is one of methanol, ethanol and isopropanol. The substrate is one of lignin, phenyl benzyl ether, phenyl phenethyl ether, diphenyl ether and lignin.
Compared with the prior art, the invention has the following technical effects:
1. the catalyst has high dispersity (average particle size of 5.8nm, shown in figures 1 and 2), high activity and good stability, takes low-carbon alcohol as a hydrogen source, and does not need additional H 2 The method can realize the high-efficiency hydrogenolysis of the lignin at a lower reaction temperature (210 ℃), and the product can be regulated and controlled.
2. The catalyst of the invention has simple preparation method, adopts a urea hydrothermal method to prepare NiAl hydrotalcite, and utilizes topological transformation to prepare NiRuAl hydrotalcite, thereby preparing high-dispersion Ni-Ru/Al hydrotalcite by in-situ reduction 2 O 3 A catalyst.
3. The invention discloses high-dispersion Ni-Ru/Al 2 O 3 The catalyst shows excellent catalytic performance in the hydrogenolysis reaction of lignin and model compounds thereof, can be used for hydrogenolysis of lignin and model compounds thereof with high selectivity and high activity under mild conditions, and is obviously superior to a commercial Ru/C catalyst.
4. The catalyst has good stability, still maintains high activity after being recycled for 5 times, is not easy to coke at high temperature, and can be separated by a magnetic field.
5. The lignin belongs to a biological refining and papermaking byproduct, and the high-efficiency conversion of the lignin has great significance for the high-valued utilization of biomass. The catalyst of the invention has simple preparation method, good stability, mild reaction condition and adjustable product, thereby having good application prospect in the process of lignin conversion.
Drawings
FIG. 1 shows Ni-Ru/Al in example 1 of the present invention 2 O 3 XRD pattern of the catalyst;
as can be seen, Ni-Ru/Al 2 O 3 The active components Ni and Ru in the catalyst are highly dispersed.
FIG. 2 shows Ni-Ru/Al in example 1 of the present invention 2 O 3 HRTEM at different magnifications of the catalyst;
from FIG. 2a, it can be seen that Ni-Ru/Al 2 O 3 The active component particles of the catalyst are distributed uniformly, and Ni-Ru/Al is obtained by measuring and calculating through a graph 2b 2 O 3 The average particle size of the active component in the catalyst was 5.8nm, also indicating a higher degree of dispersion of the active component, and it can be seen from fig. 2c that the lattice fringes of Ni (111) are consistent with the XRD analysis results.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
taking 0.02mol of Ni (NO) 3 ) 2 ·6H 2 O、0.1mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.07mol of urea, stirring and reacting for 9h at 140 ℃, centrifuging, washing, filtering and then drying in vacuum to obtain the NiAl hydrotalcite. Taking 0.5g NiAl hydrotalcite and 0.676g RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor; by H 2 Directly reducing NiRuAl hydrotalcite at 500 deg.C for 6h, cooling, and adding 1% O 2 Passivating for 1h to obtain Ni-Ru/Al 2 O 3 A catalyst. By XRD (FIG. 1) and HRTEThe M (FIG. 2) characterization indicated that Ni-Ru/Al was produced 2 O 3 The active components Ni and Ru in the catalyst are highly dispersed, and the average grain diameter is 5.8 nm. Mixing Ni-Ru/Al 2 O 3 Adding the catalyst, isopropanol and phenyl benzyl ether into a reaction kettle according to the dosage ratio of 25mg to 20mL to 100mg, sealing, filling protective gas of 1MPa, and reacting for 2h at 120 ℃ to obtain a hydrogenolysis product. The conversion of phenyl benzyl ether was 100% and the products were mainly toluene, phenol and cyclohexanol, with yields of 48.8%, 17.4% and 34.3%, respectively. After the catalyst is recycled for 5 times, the conversion rate of the phenyl benzyl ether is still up to 98.9 percent.
Example 2:
taking 0.02mol of Ni (NO) 3 ) 2 ·6H 2 O、0.1mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.07mol of urea, stirring and reacting for 12h at 130 ℃, centrifuging, washing, filtering, and drying in vacuum to obtain the NiAl hydrotalcite. Taking 0.5g of NiAl hydrotalcite and 0.676g of RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor; by H 2 Directly reducing NiRuAl hydrotalcite at 550 ℃ for 6h, cooling, and adding 1% O 2 Passivating for 1h to obtain Ni-Ru/Al 2 O 3 A catalyst. Mixing Ni-Ru/Al 2 O 3 Adding the catalyst, isopropanol and diphenyl ether into a reaction kettle according to the dosage ratio of 25mg:20mL:100mg, sealing, filling protective gas of 1MPa, and reacting at 130 ℃ for 3h to obtain a hydrogenolysis product. The conversion of diphenyl ether was 99.7%, the products were mainly benzene, cyclohexane and cyclohexanol, the yields were 8.7%, 38.3% and 51.2%, respectively.
Example 3:
taking 0.03mol of Ni (NO) 3 ) 2 ·6H 2 O、0.15mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.07mol of urea, stirring and reacting for 12h at 130 ℃, centrifuging, washing, filtering, and drying in vacuum to obtain the NiAl hydrotalcite. Taking 0.5g of NiAl hydrotalcite and 0.676g of RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor; by H 2 Direct reduction of N at 500 deg.CiRuAl hydrotalcite 6h, cooled and then treated with 1% O 2 Passivating for 1h to obtain Ni-Ru/Al 2 O 3 A catalyst. Mixing Ni-Ru/Al 2 O 3 Adding the catalyst, isopropanol and phenyl phenethyl ether into a reaction kettle according to the dosage ratio of 25mg to 20mL to 100mg, sealing, filling protective gas with 1MPa, and reacting for 4h at 110 ℃ to obtain a hydrogenolysis product. The conversion of phenyl phenethyl ether was 95.3% and the products were mainly ethylbenzene, phenol and cyclohexanol, with yields of 45.2%, 23.4% and 24.3%, respectively. Is obviously superior to the commercial Ru/C catalyst, and the conversion rate under the same conditions is only 7.7 percent.
Example 4:
taking 0.02mol of Ni (NO) 3 ) 2 ·6H 2 O、0.1mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.07mol of urea, stirring and reacting for 9h at 140 ℃, centrifuging, washing, filtering, and drying in vacuum to obtain the NiAl hydrotalcite. Taking 0.5g NiAl hydrotalcite and 0.676g RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor; by H 2 Directly reducing NiRuAl hydrotalcite at 500 ℃ for 6h, cooling and then using 1% of O 2 Passivating for 1h to obtain Ni-Ru/Al 2 O 3 A catalyst. Mixing NiRu/Al 2 O 3 Adding the catalyst, isopropanol and lignin into a reaction kettle according to the dosage ratio of 250mg to 20mL to 500 mg, sealing, filling protective gas with 1MPa, and reacting at 210 ℃ for 4 hours to obtain a hydrogenolysis product. The lignin conversion was 63.9%, the methanol solubles yield was 58.5%, wherein the monomers and dimers accounted for 69.9%, and the methanol solubles were based on phenolic compounds.
Example 5:
taking 0.02mol of Ni (NO) 3 ) 2 ·6H 2 O、0.1mol Al(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.07mol of urea, stirring and reacting for 20h at 120 ℃, centrifuging, washing, filtering, and drying in vacuum to obtain the NiAl hydrotalcite. Taking 0.5g of NiAl hydrotalcite and 0.676g of RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor; by H 2 Direct reduction at 500 deg.CCooling the original NiRuAl hydrotalcite for 6h, and then adding 1% O 2 Passivating for 1h to obtain Ni-Ru/Al 2 O 3 A catalyst. NiRu/Al is mixed 2 O 3 Adding the catalyst, isopropanol and lignin into a reaction kettle according to the dosage ratio of 250mg to 20mL to 500 mg, sealing, filling protective gas with 1MPa, and reacting at 300 ℃ for 4h to obtain a hydrogenolysis product, wherein the catalyst is hardly coked. The lignin conversion was 89.8%, and the methanol solubles yield was 72.0%, wherein the monomers and dimers accounted for 76.5%, and the methanol solubles were predominant in the hydrogenation product.

Claims (4)

1. Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 The preparation method of the catalyst is characterized by comprising the following steps:
(1) taking 0.01-0.03mol Ni (NO) 3 ) 2 ·6H 2 O、0.05-0.15molAl(NO 3 ) 3 ·9H 2 Adding 10mL of deionized water into O and 0.05-0.1mol of urea, stirring and reacting for 9-24h at 90-140 ℃, centrifuging, washing, filtering and then drying in vacuum to obtain NiAl hydrotalcite;
(2) taking 0.4-0.6g of NiAl hydrotalcite obtained in the step (1) and 0.5-0.8g of RuCl 3 ·xH 2 Adding 10mL of deionized water into O, stirring in a water bath at 60 ℃, and evaporating to remove water to obtain a NiRuAl hydrotalcite precursor;
(3) by H 2 Directly reducing the NiRuAl hydrotalcite obtained in the step (2), cooling and then using 1% of O 2 Passivating for 1-3h to obtain a target product: Ni-Ru/Al 2 O 3 A catalyst.
2. Hydrotalcite topology transition high dispersion Ni-Ru/Al according to claim 1 2 O 3 A method for producing a catalyst, characterized in that H in the step (3) 2 The reduction temperature is 450 ℃ and 600 ℃, and the reduction time is 4-8 h.
3. Hydrotalcite topology transition high dispersion Ni-Ru/Al according to claim 1 2 O 3 The application of the catalyst in the hydrogenolysis of lignin and model compounds thereof.
4. Hydrotalcite topology transition high dispersion Ni-Ru/Al according to claim 3 2 O 3 The application of the catalyst in hydrogenolysis of lignin and a model compound thereof is characterized by comprising the following steps:
mixing Ni-Ru/Al 2 O 3 Adding the catalyst, the hydrogen source and the substrate into a reaction kettle according to the dosage ratio of 20-50mg:5-20mL:50mg, sealing, filling protective gas of 1MPa, and reacting at the temperature of 100-240 ℃ for l-8h to obtain a hydrogenolysis product;
the hydrogen source is one of methanol, ethanol and isopropanol;
the substrate is one of lignin, phenyl benzyl ether, phenyl phenethyl ether and diphenyl ether.
CN202210523196.7A 2022-05-13 2022-05-13 Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use Pending CN115041190A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
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CN102631932A (en) * 2011-02-14 2012-08-15 中国科学院大连化学物理研究所 Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof
CN106423199A (en) * 2016-09-06 2017-02-22 北京化工大学 Preparation method and catalytic application of supported high-dispersity NiRu bimetallic catalyst
CN108586194A (en) * 2018-01-26 2018-09-28 中南民族大学 A kind of catalyst and preparation method thereof and the application in cracking restores aryl ethers compounds
CN112479823A (en) * 2020-11-04 2021-03-12 华东理工大学 Method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin or lignin oil
CN113171792A (en) * 2021-04-12 2021-07-27 华南理工大学 Aluminum modified molecular sieve loaded bimetallic catalyst, preparation thereof and application thereof in lignin depolymerization by hydrogenation
CN114029070A (en) * 2021-12-13 2022-02-11 安徽工业大学 In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof
CN114177930A (en) * 2021-11-09 2022-03-15 华南理工大学 Method for catalyzing lignin hydrogenation depolymerization by molecular sieve supported ruthenium-nickel catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102631932A (en) * 2011-02-14 2012-08-15 中国科学院大连化学物理研究所 Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof
CN106423199A (en) * 2016-09-06 2017-02-22 北京化工大学 Preparation method and catalytic application of supported high-dispersity NiRu bimetallic catalyst
CN108586194A (en) * 2018-01-26 2018-09-28 中南民族大学 A kind of catalyst and preparation method thereof and the application in cracking restores aryl ethers compounds
CN112479823A (en) * 2020-11-04 2021-03-12 华东理工大学 Method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin or lignin oil
CN113171792A (en) * 2021-04-12 2021-07-27 华南理工大学 Aluminum modified molecular sieve loaded bimetallic catalyst, preparation thereof and application thereof in lignin depolymerization by hydrogenation
CN114177930A (en) * 2021-11-09 2022-03-15 华南理工大学 Method for catalyzing lignin hydrogenation depolymerization by molecular sieve supported ruthenium-nickel catalyst
CN114029070A (en) * 2021-12-13 2022-02-11 安徽工业大学 In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof

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